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WO2025032494A1 - Procédé de production de dioxyde de titane à partir d'un matériau d'anode de batteries au titanate de lithium usagées - Google Patents

Procédé de production de dioxyde de titane à partir d'un matériau d'anode de batteries au titanate de lithium usagées Download PDF

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Publication number
WO2025032494A1
WO2025032494A1 PCT/IB2024/057595 IB2024057595W WO2025032494A1 WO 2025032494 A1 WO2025032494 A1 WO 2025032494A1 IB 2024057595 W IB2024057595 W IB 2024057595W WO 2025032494 A1 WO2025032494 A1 WO 2025032494A1
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WO
WIPO (PCT)
Prior art keywords
titanium dioxide
range
anode
residue
defmed
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/IB2024/057595
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English (en)
Inventor
Smruti PRAKASH BARIK
G. Prabaharan
Bhuvnesh KUMAR
Amit Kulkarni
Nitin Gupta
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Attero Recycling Pvt Ltd
Original Assignee
Attero Recycling Pvt Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
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Publication of WO2025032494A1 publication Critical patent/WO2025032494A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B1/00—Preliminary treatment of ores or scrap
    • C22B1/02—Roasting processes
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00—Compounds of titanium
    • C01G23/04—Oxides; Hydroxides
    • C01G23/047—Titanium dioxide
    • C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
    • C22B26/10—Obtaining alkali metals
    • C22B26/12—Obtaining lithium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B34/00—Obtaining refractory metals
    • C22B34/10—Obtaining titanium, zirconium or hafnium
    • C22B34/12—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08
    • C22B34/1204—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 preliminary treatment of ores or scrap to eliminate non- titanium constituents, e.g. iron, without attacking the titanium constituent
    • C22B34/1213—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 preliminary treatment of ores or scrap to eliminate non- titanium constituents, e.g. iron, without attacking the titanium constituent by wet processes, e.g. using leaching methods or flotation techniques
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B34/00—Obtaining refractory metals
    • C22B34/10—Obtaining titanium, zirconium or hafnium
    • C22B34/12—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08
    • C22B34/1236—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining titanium or titanium compounds from ores or scrap by wet processes, e.g. by leaching
    • C22B34/124—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining titanium or titanium compounds from ores or scrap by wet processes, e.g. by leaching using acidic solutions or liquors
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B34/00—Obtaining refractory metals
    • C22B34/10—Obtaining titanium, zirconium or hafnium
    • C22B34/12—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08
    • C22B34/1236—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining titanium or titanium compounds from ores or scrap by wet processes, e.g. by leaching
    • C22B34/124—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining titanium or titanium compounds from ores or scrap by wet processes, e.g. by leaching using acidic solutions or liquors
    • C22B34/125—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining titanium or titanium compounds from ores or scrap by wet processes, e.g. by leaching using acidic solutions or liquors containing a sulfur ion as active agent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B34/00—Obtaining refractory metals
    • C22B34/10—Obtaining titanium, zirconium or hafnium
    • C22B34/12—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08
    • C22B34/1236—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining titanium or titanium compounds from ores or scrap by wet processes, e.g. by leaching
    • C22B34/1259—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining titanium or titanium compounds from ores or scrap by wet processes, e.g. by leaching treatment or purification of titanium containing solutions or liquors or slurries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/54—Reclaiming serviceable parts of waste accumulators
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/80—Compositional purity
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B21/00—Obtaining aluminium
    • C22B21/0015—Obtaining aluminium by wet processes
    • C22B21/0023—Obtaining aluminium by wet processes from waste materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy

Definitions

  • the present invention relates to the field of spent lithium-ion batteries. More particularly, the present invention relates to a process for production of titanium dioxide from an anode material of spent lithium titanate batteries.
  • lithium-ion batteries The number of lithium-ion batteries (LIBs) is steadily increasing in order to meet the evergrowing demand for sustainable energy and a high quality of life for humankind.
  • the resulting battery waste certainly poses safety hazards if not handled properly.
  • Current commercial lithium ion batteries mainly contain transition metal oxides or phosphates, aluminum, copper, graphite, organic electrolytes containing harmful lithium salts and other chemicals. Therefore, the reuse and recycling of spent lithium ion batteries has been paid more and more attention by many researchers.
  • the recycling of waste lithium ion batteries has great difficulties.
  • Spent lithium ion batteries include many valuable metals, such as lithium (Li), cobalt (Co), nickel (Ni), manganese (Mn), iron (Fe), copper (Cu) and aluminum (Al).
  • the composition of these metals is not only similar to natural minerals, but the content of them is even higher than that of natural minerals. Consequently, the precious resource of spent LIBs should not be treated as waste in consideration of strategic materials and sustainable development. In addition to alleviating the shortages of raw materials, the recovery and reuse of spent lithium ion batteries (LIBs), can also bring huge economic value.
  • CN111020194A discloses a method for synthesizing a titanium aluminum alloy from waste lithium titanate positive and negative electrode powder.
  • the method comprises the steps of: reduction leaching of the waste lithium titanate positive and negative electrode powder; copper separation and purification of leaching filtrate and two-step iron and aluminum removal; deep impurity removal of iron and aluminum removing liquid and step-by-step extraction of rare and noble metal cobalt and nickel; separation and purification of iron and aluminum removing slag and extraction of aluminum hydroxide; evaporation and lithium extraction of raffmate and titanium extraction; mixed calcination of metatitanic acid and aluminum hydroxide and fused salt electrolysis of titanium aluminum oxide.
  • WO20 17215282 Al discloses a method for recycling of lithium in anode material of a lithium battery by means of an electrochemical process.
  • This citation provides a method for recycling lithium in an anode material of a lithium battery by means of an electrochemical process.
  • the anode material of the lithium battery serves as an anode
  • a metal or carbon electrode serves as a cathode
  • an aqueous solution serves as an electrolyte
  • lithium ions in the anode material of the lithium battery are transferred to the electrolyte aqueous solution to form lithium containing solution.
  • This citation is focused on recycling of lithium from an anode material of a lithium battery.
  • Kishore K. Jena et. al. (Energy Fuels, 35, 18257-18284), reported about battery chemistry, degradation mechanism, pretreatment processes and pyro metallurgical and hydrometallurgical methods.
  • TiCoO 2 with inorganic acid produces Cl 2 , SO 2 , and NO 2 gases, which have adverse impacts on the environment. These gases react with moisture in the air to produce H 2 SO 4 , HNO 3 and HC1 acid molecules that later form acid rain.
  • the present invention is an endeavor in this direction
  • the main object of the present invention is to provide a process for the production of titanium dioxide from spent lithium titanate batteries.
  • Another object of the present invention is to provide a process for the production of titanium dioxide from anode material of spent lithium titanate batteries
  • Yet another object of the present invention is to provide a commercially feasible method for producing pure titanium dioxide from waste/spent lithium titanate batteries.
  • Yet another object of the present invention is to provide a method that ensures greater recovery (> 98%) of titanium with (>99%) purity of titanium dioxide.
  • Still another object of the present invention is to provide a method that is clean, green, and environmentally friendly.
  • the present invention relates to a method for producing titanium dioxide from anode material of spent lithium ion battery.
  • the method is simple, easy to operate and economically attractive.
  • the recovery of titanium dioxide from spent lithium titanate barriers is a chemical free process.
  • the present invention provides a process for production of titanium dioxide from anode material of spent lithium titanate batteries, characterized in that, the method comprising the steps of: (a) treating an anode material of spent lithium titanate batteries with a suitable solution to remove an anode powder from an aluminium foil; (b) mixing the anode powder obtained in step (a) with a suitable acid and pugging at a predefined temperature for a pre-defmed time to obtain a pugged anode powder; (c) leaching the pugged anode powder obtained in step (b) by agitating with a suitable acid to maintain the pH in a pre-determined range, for 2- 4 hours with a pre-defmed solid-liquid ratio to obtain a slurry; (d) filtering the slurry obtained in step (c) to obtain a leach liquor for lithium recovery and a residue-I; (e) washing the residue-I obtained in step (d) with water followed by filtration to get a washed liquor and a residue-II
  • Figure 1 is a schematic representation for the production of titanium dioxide form anode material of spent lithium titanate batteries according to an embodiment of the present invention.
  • the present invention provides a method for producing titanium dioxide from anode material of spent lithium ion battery.
  • the method is simple, easy to operate and economically attractive.
  • the recovery of titanium dioxide from spent lithium titanate barriers is a chemical free process.
  • the present invention provides a process for production of titanium dioxide from anode material of spent lithium titanate batteries, characterized in that, the method comprising the steps of: (a) treating an anode material of spent lithium titanate batteries with a suitable solution to remove an anode powder from an aluminium foil; (b) mixing the anode powder obtained in step (a) with a suitable acid and pugging at a pre-defmed temperature for a pre-defmed time to obtain a pugged anode powder; (c) leaching the pugged anode powder obtained in step (b) by agitating with a suitable acid to maintain the pH in a pre-determined range, for 2- 4 hours with a pre-defmed solid-liquid ratio to obtain a slurry; (d) filtering the slurry obtained in step (c) to obtain a leach liquor for lithium recovery and a residue-I; (e) washing the residue-I obtained in step (d) with water followed by filtration to get a washed liquor and
  • the anode material of step (a) is an anode foil and the suitable solution of step (a) is sodium hydroxide (NaOH) solution (0.5%-2% w/v).
  • the suitable acid of step (b) is selected from nitric acid (HNO 3 (0.5-0.9 w/w)) or sulphuric acid (H 2 SO 4 (0.3 - 0.6 w/w)).
  • the pre-determined temperature of step (b) is in a range of 100°C to 200°C and the pre-defmed time of step (b) is in a range of 4-8 hours.
  • the suitable acid of step (c) is selected from 5-10% nitric acid (HNO 3 ) or 5-10% sulphuric acid (H 2 SO 4 ).
  • pre-determined temperature of step (f) is in a range of 700-1000°C and the pre-defmed time of step (f) is in a range of 6-8 hours.
  • the leach liquor obtained in step (d) is sent to a lithium recovery section.
  • FIG. 1 shows a process flow sheet for the production of titanium dioxide from anode material of spent lithium titanate batteries.
  • the residue-I was washed with 0.18 L of water and the wash liquor was kept separately to use in the next batch for leaching.
  • the residue-II (0.163 kg) obtained after washing was roasted at 800°C for 8 hours to get the pure titanium dioxide (0.145 kg).
  • the chemical analysis of anode mass, pugged material, leach liquor and residue-II were shown in Table 1.
  • the residue-I was washed with 0.9 T water and the wash liquor was kept separately to use in the next batch for leaching.
  • the residue -II (0.80 kg) obtained after washing was roasted at 900°C for 6 hours to get the pure titanium dioxide (0.718 kg).
  • the chemical analysis of anode mass, pugged material, leach liquor, and residue-II were shown in Table 2.
  • the present invention provides a simple, easy to operate and cost effective method for production of titanium dioxide from anode material of spent lithium titanate batteries.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Geology (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • General Chemical & Material Sciences (AREA)
  • Electrochemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Abstract

La présente invention se rapporte au domaine des batteries au lithium-ion usagées. Plus particulièrement, la présente invention concerne un procédé de production de dioxyde de titane à partir d'un matériau d'anode de batteries au titanate de lithium usagées d'une manière commercialement réalisable. Le procédé permet la récupération du titane (> 98 %) avec une pureté (> 99 %) du dioxyde de titane. Le procédé est simple, facile à utiliser et économique du fait qu'un procédé sans produits chimiques est utilisé pour la récupération.
PCT/IB2024/057595 2023-08-09 2024-08-06 Procédé de production de dioxyde de titane à partir d'un matériau d'anode de batteries au titanate de lithium usagées Pending WO2025032494A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
IN202311053428 2023-08-09
IN202311053428 2023-08-09

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WO2025032494A1 true WO2025032494A1 (fr) 2025-02-13

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PCT/IB2024/057595 Pending WO2025032494A1 (fr) 2023-08-09 2024-08-06 Procédé de production de dioxyde de titane à partir d'un matériau d'anode de batteries au titanate de lithium usagées

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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109896544A (zh) * 2019-01-30 2019-06-18 江西赣锋循环科技有限公司 回收废旧钛酸锂负极材料制备冶金用二氧化钛和电池级碳酸锂的方法

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109896544A (zh) * 2019-01-30 2019-06-18 江西赣锋循环科技有限公司 回收废旧钛酸锂负极材料制备冶金用二氧化钛和电池级碳酸锂的方法

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
TANG WENJIANG, CHEN XIANGPING, ZHOU TAO, DUAN HAO, CHEN YONGBIN, WANG JIAN: "Recovery of Ti and Li from spent lithium titanate cathodes by a hydrometallurgical process", HYDROMETALLURGY., ELSEVIER SCIENTIFIC PUBLISHING CY. AMSTERDAM., NL, vol. 147-148, 1 August 2014 (2014-08-01), NL , pages 210 - 216, XP093280065, ISSN: 0304-386X, DOI: 10.1016/j.hydromet.2014.05.013 *
YAO YONGLIN, ZHU MEIYING, ZHAO ZHUO, TONG BIHAI, FAN YOUQI, HUA ZHONGSHENG: "Hydrometallurgical Processes for Recycling Spent Lithium-Ion Batteries: A Critical Review", ACS SUSTAINABLE CHEMISTRY & ENGINEERING, AMERICAN CHEMICAL SOCIETY, US, vol. 6, no. 11, 5 November 2018 (2018-11-05), US , pages 13611 - 13627, XP093016053, ISSN: 2168-0485, DOI: 10.1021/acssuschemeng.8b03545 *

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